Single-solution adhesive resin formulations

ABSTRACT

Single-solution adhesive resin formulations are made of predominantly dimethacrylates or diacrylates containing (predominantly) two carboxy groups and a functionalized methacrylate or acrylate diluent monomer. A novel light-activated initiator can be used for photopolymerization of such adhesives.

This invention was made under National Institute of Dental Researchgrant R37 DE05129-19 and P50 DE09322-07 from the National Institutes ofHealth. The government therefore retains certain rights in theinvention.

This application is a Continued Prosecution Application of applicationSer. No. 09/019,604 filed Feb. 6, 1998.

BACKGROUND OF THE INVENTION

Most bonding systems that contain carboxylated monomers for priming andhydrophilic monomers for bonding require a number of consecutiveprocedural steps after conditioning with an acid which are aimed atoptimizing the adhesion to dentin. These include (1) mixing of a primermonomer with a comonomer/co-initiator, usually a secondary or tertiaryaromatic amine, e.g. mono- or bivalent salts of bis-(N-tolyl glycineglycidyl methacrylate) and (2) priming of the prepared dentin surfacewith this mixture (Bowen, 1985; Bowen, 1986; Bowen, 1987; Venz andDickens, 1991; Venz and Dickens, 1993; Bowen, 1993; Bowen, 1994; Ibsenet al., 1994; Suh et al., 1994). The third step comprises application ofan unfilled bonding resin, which will then be light-cured. The bondingresin consists mainly of2,2-bis[p(2'-hydroxy-3'-methacryloxypropoxy)phenylene]-propane (bis-GMA)and 2-hydroxyethyl methacrylate (2-HEMA).

A different approach was taken by Waknine (1992) who disclosed athree-step adhesive system that contains a nonacidic carbonate monomerinstead of the carboxylated resin and a different type of amineaccelerator. The bond strengths reported by Waknine are on the order ofabout 10 Mpa.

Recently, abstracts describing bonding to dentin with one-component(better described as one-solution) adhesive resin systems have beenreported (Jia et al., 1996; Kelsey et al., 1996; Latta et al., 1996;Qian et ai, 1996; Dickens et al., 1997). More recently, a patent (Qianet at, August 1997, U.S. Pat. No. 5,658,963) has been issued describingone-step formulations. These adhesive resin formulations comprise in asingle solution the components that were applied in the multistep systemin several sequential steps as described above. The components are: thebonding resin consisting of a viscous monomer, bis-GMA, and the diluentmonomer 2-HEMA, as well as light-sensitive polymerization catalysts, anamine accelerator, and acetone and/or ethanol as the solvent(s).

Various U.S. patents disclose use of other one-solution systems. Bunkerand Fields, (1985); Aasen, (1988); Bunker, (1994) describe polymerizablephosphate esters. However, these bonding systems yielded a relativelylow bond strength to dentin of about 9 MPa. Also, these bonding systemscontain a multitude of polymerizable components in their systems, amongwhich are phosphate esters. These esters can hydrolyze, thus releasingfree acid, which can, in turn, lead to hydrolysis of methacrylate estersresulting in the release of methacrylic acid and loss of thepolymerizable functionality on the resin. Thus, phosphate esters areless stable than the carboxylic acid esters described in this invention.Bunker et al. (1985), reported mixing the adhesive with a solution ofsodium benzene sulfinate as a coinitiator, which adds another step tothese so-called one-step formulations.

James (1987) describes adhesive compositions for tooth enamel, but doesnot teach adhesion to dentin.

Blackwell and Huang (1987, 1989) and Huang and Blackwell (1990) describephosphate esters of mono- or dipentaerytliritol. However, use of theexperimental formulations reported by Blackwell and Huang (1987, 1989)resulted in relatively low bond strengths to dentin (about 8.4 MPa).Higher bond strengths were reported by Huang and Blackwell (1990) butonly if an unfilled bonding resin was applied as a second step afterpriming. Also, the storage stability of these phosphate-containingresins was less than desirable, possibly due to the above describedhydrolysis of the ester group.

There is a need in the art for new methods and compositions foradhesives for use in restoring teeth in which the bond strength is good,the steps and reagents are kept to a minimum, and the time required forthe restoration is short.

SUMMARY OF THE INVENTION

It is an object of the invention to provide an adhesive resinformulation.

It is another object of the invention to provide a method of bonding acomposite resin to a prepared surface.

It is still another object of the invention to provide a method ofproducing a formulation for bonding a composite resin to a preparedsurface.

It is yet another object of the invention to provide kits for bonding acomposite resin to a prepared surface.

These and other objects of the invention are provided by one or moreembodiments described below. In one embodiment a single-solutionadhesive resin formulation for bonding a composite resin to enamel,dentin or nonprecious metal is provided. The formulation can also beused for bonding a ceramic or a nonprecious metal to dentin. Theformulation comprises: not more than two polymerizable monomers and aphotoinitiator, wherein a first of the two monomers is an acidic monomerand the second of the two monomers is a diluent monomer.

In another embodiment of the invention a single-solution adhesive resinformulation for bonding a composite resin to enamel, dentin ornonprecious metal is provided. The formulation can also be used forbonding a ceramic or a nonprecious metal to dentin. The formulationcomprises: not more than two polymerizable monomers, a solvent, and aphotoinitiator, wherein a first of the two monomers is pyromelliticglycerol dimethyacrylate (PMGDM) monomer, the second of the two monomersis 2-HEMA monomer, and the photoinitiator is 2, 4,6-trimethylbenzoyldiphenylphosphine oxide.

In another embodiment of the invention a method of bonding a compositeresin to enamel dentin or nonprecious metal is provided. The method canalso be used for bonding a ceramic or a nonprecious metal to dentin. Themethod comprises: applying an adhesive resin formulation onto a preparedsurface selected from the group consisting of enamel, dentin ornonprecious metal; air drying the adhesive resin formulation; repeatingthe steps of applying and air drying between 0 and 2 times;photopolymerizing the adhesive resin formulation; contacting theformulation with a composite resin; and photopolymerizing the compositeresin to form a bond having a shear bond strength of at least 20 MPa.

According to another aspect of the invention a method of producing aformulation for bonding a composite resin to enamel, dentin, ornonprecious metal, or a ceramic or a non-precious metal to dentin, isprovided. The formulation can also be used for bonding a ceramic or anonprecious metal to dentin. The method comprises the step of: combiningnot more than two monomers and a photoinitiator, wherein a first of thetwo monomers is an acidic monomer and the second of the two monomers isa diluent monomer.

In yet another embodiment of the invention a kit for bonding a compositeresin to enamel, dentin or metal is provided. The kit can also be usedfor bonding a ceramic or a nonprecious metal to dentin. The methodcomprises:

a formulation which comprises not more than two monomers and aphotoinitiator, wherein a first of the two monomers is a carboxylic acidmonomer and the second of the two monomers is a diluent monomer, and acomposite resin.

The present invention thus provides the art with a single-solutionadhesive resin formulation for bonding to enamel, dentin, or nonpreciousmetal, or for bonding a ceramic or a nonprecious metal to dentin. Thisformulation simplifies and economizes the bonding procedure by allowingapplication of the bonding system to conditioned tooth surfaces or tononprecious metal surfaces in a single step, in contrast to themultistep procedure employed in conventional systems.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It is a discovery of the present inventor that a successful adhesiveresin formulation can be made by simply combining a single acidic primermonomer with a single functionalized diluent monomer in a solvent. Themixture preferably also contains a photoinitiator (camphorquinone) and atertiary amine accelerator (such as 4-N,N-(dimethylamino)benzoate(4-EDMAB), or, as an alternative, a photoinitiator that does not requirean amine accelerator as does camphorquinone. The solution can be paintedonto the dentin once, air dried and then optionally applied two moretimes, gently dried and photopolymerized. In addition to the time savedby the dental practitioner by requiring only one solution to prepare thetooth surface for bonding, this solution comprises only two resincomponents and the solvent, as opposed to three resin components andsolvent employed in conventional multistep systems.

The alternative photoinitiator employed here does not require a tertiaryamine accelerator. Tertiary amine accelerators may contribute tounwanted radical formation by the acidic monomers during storage. Theymay also cause premature curing of the formulation, which results indecreased shear bond strengths of up to 30% after storage of the bondingsolution at elevated temperatures (37° C.) for several months (U.S. Pat.No. 5,658,963, at Example 27). Thus elimination of tertiary aminesgreatly improves the shelf life of the single-solution adhesive resinsystem.

The present invention is based on only two polymerizable monomers, asopposed to three monomers described in U.S. Pat. No. 5,658,963. Acidicmonomers which can be used include carboxylic acid monomers,pyromellitic dianhydride-HEMA adduct (PMDM), pyromellitic glyceroldimethyacrylate (PMGDM), biphenyl dianhydride-HEMA adduct (BPDM),3,3'-4,4'-tetracarboxylic dianhydride (BPGDM) and5-(2,5-dioxotetrahydro-3-furanyl)-3-cyclohexene-1,2-dicarboxylicanhydride glycerol dimethacrylate adduct (B4400-GDM). Diluent monomersinclude 2-hydroxyethylmethyacrylate, glycerol dimethacrylate (GDM),ethyl-α-hydroxymethyl acrylate (Ed), and tetrahydro furfurylmethacrylate(THFM). Selection of suitable monomers is well within the skill of theart. The adhesive resin systems of the present invention yield bondstrengths between 20 and 40 MPa. These compare favorably with prior artone-solution formulations (One-step; Bisco Inc.), which were reported tohave dentin shear bond strengths between 22 MPa and 30 MPa, and bondstrengths to enamel or nonprecious metal of 27 MPa to 28 MPa (U.S. Pat.No. 5,658,963, at Examples 1-24).

Photoinitiators for polymerization of the adhesive resin can be anyknown in the art, such as camphorquinone and a tertiary amine. Thephotoinitiator preferably employed in this invention is2,4,6-trimethylbenzoyldiphenylphosphine oxide, also known asphotoinitiator 8728 (Ward Blenkinsop, Cheshire, UK). It is an acylphosphine oxide. Reactions of various phosphines with olefinic doublebonds have been reported by Morgan et al. as early as 1978. Use ofacylphosphine oxides as photoinitiators have been reported in variousGerman patents (Nos. 2,830,927 and 2,909,994) and in U.S. Pat. No.4,710,523. An acylphosphine compound for use in polyene-polythiol dentalimpression compositions has been described in U.S. Pat. No. 5,100,929.However, monoacylphosphine oxides do not cure composite resins to agreat depth; they cause a rather shallow curing. This is mainly due totheir maximum absorbance at about 380 nm, which is a considerablyshorter wavelength than that at which camphorquinone has its maximumabsorbance. The absorbance of camphorquinone at 470 nm causescamphorquinone/tertiary amine-activated composite resins to cure after20 s irradiation to a depth of about 5.2 mm compared to 2.9 mm for themonoacylphosphine oxide-activated composite resin. However, use of themonoacyiphosphine oxides as initiators for adhesive resin systems asdescribed in this invention does not require a significant curing depth,since adhesive resins are usually applied in thin layers up to athickness of 200 μm. Monoacylphosphine oxides have not been usedpreviously in adhesive resin systems. Bis-acyiphosphine oxides have beendescribed in European Patent No. 184 095. Since they absorb at aslightly higher wavelength than the monoacylphosphine oxides, theirdepth of cure is somewhat greater and they can be used in conventionaldental composite resins.

Conditioning of dentin or enamel prior to the application of thesingle-solution adhesive resin system of the present invention can beachieved by any method known in the art. For example, etching withphosphoric acid can be used, as is conventional. Alternatively, apolymerizable conditioner can be used as described by Dickens (1996).Nonprecious metals which can be used as substrates for the adhesiveresin system include nickel-chromium alloys (e.g., Rexildium®, andchromium cobalt alloys).

The adhesive resin PMGDM can be prepared from 1 part pyromelliticdianhydride (PMDA) and two parts glycerol dimethacrylate (GDM). Thepreferred ratio of PMDA to GDM is 1:2.05 giving a slight excess of GDMto avoid the remaining of unreacted toxic dianhydride.

The following examples are provided for exemplification purposes onlyand are not intended to limit the scope of the invention which has beendescribed in broad terms above.

METHODS USED IN THE EXAMPLES

Sample preparation

Dentin samples were prepared and tested by following the procedureoutlined by Venz and Dickens (1993). Extracted, noncarious human molarsthat had been stored in 0.2% sodium azide at 5° C. were cut with aslowly rotating diamond blade (Isomet, Buehler Ltd., Lake Bluff, IL)under running water until a smooth dentin surface was exposed. The humanteeth with exposed coronal dentin, bovine enamel slabs or castRexillium® (Jeneric/Pentron, Inc., Wallingford, Conn.) stubs for testingadhesion to metal were mounted in cylindrical polycarbonate holders withself-curing acrylic. The dentin and enamel specimens were stored indistilled water at room temperature until they were used for bonding.Prior to bonding all specimens were ground under water irrigation on 320grit SiC paper to generate standardized surface conditions. The metalspecimens were then sandblasted with 50 μm Al₂ O₃ powder and rinsedtwice with 95% ethanol.

Bonding protocol

The conditioners used to prepare the tooth surfaces prior to theapplication of the adhesive resin system were either 37%¹ phosphoricacid gel (Myron International, Kansas City, Kans.), the polymerizableconditioner PYROMELLITICBIS-[P(2'-HYDROXY-3'-METHACRYLOXY-PROPOXY)PHENYLENE]PROPANE, which is amonomer that has been synthesized from a bifunctional dimethacrylateresin and a carboxylic acid dianhydride, or PYROMELLITICBIS-[P(2'-HYDROXY-3'-METHACRYLOXY-PROPOXY)PHENYLENE]PROPANE combinedwith vinyl phosphonic acid. The phosphoric acid gel was rinsed off after20 seconds. The polymerizable conditioners were agitated on the toothsurfaces for 1 minute and then rinsed. After removing excess water, allsurfaces were kept under moist tissue paper. Two drops of thesingle-solution adhesive were dispensed into a well. A small brushsaturated with the solution was pressed with circular movements againstthe tooth surface, thus allowing the solvent to evaporate during theagitation. A short blast of air was used to speed up the evaporation ofthe solvent. After that two more applications with the applicator brushwere applied, followed by careful drying to remove residual solventwithout blowing the resin off the surface. The control (multistep)treatment comprised the following steps: The priming resin PMGDM whichis the addition product of pyromellitic dianhydride and glyceroldimethacrylate (Venz and Dickens, 1991 and 1993), was activated bycombining 40 μL (two drops) of 20% PMGDM in acetone and 20 μL (one drop)of 5% of the polymerization catalyst, magnesium bis-(N-p-tolylglycineglycidylmethacrylate) [Mg(NTG-GMA)₂ ] in acetone in a dappen dish. Fivecoatings of the mixture were painted onto the tooth surface, allowingthe acetone to evaporate between applications. After five coats theprimed surface was carefully dried to remove residual solvent. Afterapplication of the activated PMGDM, photopolymerizable unfilled resinwas dabbed on the primed surfaces, thinned with an air stream andlight-cured for 20 s with a commercial dental curing light (the MAX,Caulk/Dentsply, Milford, Del.). A TEFLON®-coated metal iris with aninternal diameter of 4 mm was placed directly on the treated surface.The cavity in the iris was filled with composite (APH, Caulk/Dentsply,Milford, Del.), which was then irradiated for 1 min with the curinglight. The assembly was left undisturbed for an additional 4 min andthen stored in distilled water for 24 h at room temperature prior totesting in shear mode at a cross-head speed of 0.5 mm per min.

EXAMPLE 1

Shear bond strengths to dentin mediated by the single-solutionformulation were evaluated after phosphoric acid conditioning andcompared to the multi-step control.

    ______________________________________                                        Dentin Shear Bond Strengths (SBS) in MPa with the                               Single-Solution Adhesive Resin System                                                                   Second                                              Adhesive Resin composition (separate) SBS in MPa                              system in acetone (first step) step mean (n = 5) sd*                        ______________________________________                                        Single-solution                                                                        33% PMGDM.sup.#                                                                              none     25 ± 5                                      A 10% 2-HEMA                                                                  Single-solution 38% PMGDM.sup.# none 26 ± 4                                B 5% 2-HEMA                                                                   Single-solution 33% PMGDM.sup.# none 22 ± 4                                C 10% THFM.sup.a                                                              Single solution 38% PMGDM.sup.# none 20 ± 2                                D 5% THFM                                                                     Multistep 20% PMGDM.sup.## Unfilled 25 ± 7                                 (Control) 5% Mg(NTG- Bonding                                                   GMA).sup.2 resin                                                           ______________________________________                                         dentin was conditioned with 37% phosphoric acid gel                           .sup.# all singlesolution resins were activated with 0.2% camphorquinone      and 0.8% 4EDMAB;                                                              .sup.## the multistep primer was activated with 0.2% camphorquinone and 2     benzoyl peroxide                                                              *standard deviation                                                           .sup.a tetrahydrofurfuryl methacrylate                                   

EXAMPLE 2

The experiments with single-solution adhesives A to D from Example 1were repeated.

    ______________________________________                                        Dentin Shear Bond Strengths (SBS) in MPa with the                               Single-Solution Adhesive Resin System                                                                   Second                                               Resin composition (separate) SBS in MPa                                      Adhesive system in acetone (first step) step mean (n = 7) sd*               ______________________________________                                        Single-solution A                                                                       33% PMGDM.sup.#                                                                             none     35 ± 5                                       10% 2-HEMA                                                                   Single-solution B 38% PMGDM.sup.# none 27 ± 7                               5% 2-HEMA                                                                    Single-solution C 33% PMGDM.sup.# none 25 ± 6                               10% THFM.sup.a                                                               Single solution D 38% PMGDM.sup.# none 27 ± 6                               5% THFM                                                                    ______________________________________                                         dentin was conditioned with 37% phosphoric acid gel                           .sup.# all singlesolution resins were activated with 0.2% camphorquinone      and 0.8% 4EDMAB;                                                              *standard deviation                                                           .sup.a tetrahydrofurfuryl methacrylate                                   

EXAMPLE 3

The experiments with single-solution adhesive A (33% PMGDM and 10%2-HEMA) were repeated using either phosphoric acid gel or thepolymerizable conditioner PMBGA for conditioning. The single-solutionadhesive A was activated either with camphorquinone and 4-EDMAB orLucerin 8728.

    ______________________________________                                        Dentin Shear Bond Strengths (SBS) in MPa with                                   Single-Solution Adhesive Resin System A                                       (33% PMGDM and 10% 2-HEMA) varying the                                        Photoinitiator and the Conditioner                                            System                           SBS in MPa                                   Code Photoinitiator Conditioner mean (n = 5) sd*                            ______________________________________                                        A/CQ-ED                                                                              0.2% camphorquinone                                                                         PMBGA       36 ± 6                                       0.8% 4-EDMAB                                                                 A/LR 1% Lucerin 8728 PMBGA 36 ± 5                                          A/CQ-ED 0.2% camphorquinone 37% phosphoric 36 ± 4                           0.8% 4-EDMAB acid gel acid                                                   A/LR 1% Lucerin 8728 37% phosphoric 39 ± 4                                   acid gel                                                                  ______________________________________                                         *standard deviation                                                      

EXAMPLE 4

Single-Solution Adhesive Resin System A (33% PMGDM and 10% 2-HEMA)activated with Lucerin 8728 was tested on the nonprecious metalRexillium® and on bovine enamel, which was conditioned with thepolymerizable conditioner PMBGA+vinyl phosphonic acid as described inthe Patent Application Ser. No. 08/785,174 (Dickens, 1997).

    ______________________________________                                        Shear Bond Strengths (SBS) to Enamel and Metal with Single-                     Solution Adhesive Resin System A/LR (33% PMGDM and 10%                        2-HEMA, activated with 1% Lucerin 8728)                                                       SBS in MPa                                                    Substrate mean (n = 5) sd*                                                  ______________________________________                                        Rexillium ®                                                                             27 ± 5                                                         Bovine Enamel 35 ± 9                                                     ______________________________________                                         *standard deviation                                                      

EXAMPLE 5

Single-Solution Adhesive Resin System A (33% PMGDM and 10% 2-HEMA)activated with Lucerin 8728, Lucerin TPO or Darocur 4265, atwo-component photoinitiator was tested on dentin.

    ______________________________________                                        Shear Bond Strengths (SBS) to Dentin                                                           SBS in MPa                                                     mean (n = 5) sd*                                                            ______________________________________                                        System A/Lucerin 8728                                                                          37 ± 9                                                      System A/Darocur 4265 41 ± 12                                              System A/Lucerin TPO 37 ± 12                                             ______________________________________                                         *standard deviation                                                      

EXAMPLE 6

Shear bond strengths to phosphoric acid-conditioned dentin mediated bythe Single-Solution Adhesive System A, which was activated with LucerinTPO. In this example the adhesive was applied in either 1, 2, or 3applications with the applicator brush; irradiation times were 10 s or20 s, respectively.

    ______________________________________                                        Dentin Shear Bond Strengths (SBS) in MPa with the Single-Solution              Adhesive System A, activated with Lucerin TPO.                                               SBS in MPa (mean** ± SD*)                                  No. of applications                                                                           10 seconds                                                                              20 seconds                                          ______________________________________                                        1               30 ± 13                                                                              28 ± 8                                             2 37 ± 2   34 ± 10                                                      3 36 ± 14 31 ± 4                                                      ______________________________________                                         dentin was conditioned with 37% phosphoric acid gel                           **n = 4 for each group;                                                       *standard deviation                                                      

EXAMPLE 7

Shear bond strengths to phosphoric acid-conditioned dentin mediated bynonaged and aged (4 days at 45.8° C.) Single-Solution Adhesive System A,which was activated with Lucerin TPO or camphorquinone and tertiaryamine. In this example, the adhesive was applied in 2 applications withthe applicator brush; irradiation times were 10 s.

    ______________________________________                                        Dentin Shear Bond Strengths (SBS) in MPa with the Single-Solution              Adhesive System A, activated with Lucerin TPO.                                                 SBS in MPa (mean** ± SD*)                                No. of applications                                                                             nonaged   aged                                              ______________________________________                                        System A/Lucerin/TPO.sup.#                                                                      37 ± 12                                                                              39 ± 10                                          System A2/Lucerin/TPO.sup.## 46 ± 11 36 ± 7                             System A2/Lucerin/CQ-4-ED.sup.## 31 ± 8  32 ± 15                      ______________________________________                                         .sup.# aged for 4 days at 46° C.                                       .sup.## aged for 7 days at 42° C.                                      **n = 5 for each group;                                                       *standard deviation                                                      

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I claim:
 1. A single-solution adhesive resin formulation for bonding acomposite resin to enamel, dentin or nonprecious metal, or for bonding aceramic or a nonprecious metal to dentin, comprising:not more than twopolymerizable monomers and an initiator consisting of a photoinitiator,wherein a first of the two monomers is an acidic monomer and the secondof the two monomers is a diluent monomer, wherein polymerization of saidmonomers forms a bond having a shear bond strength of at least 20 MPa.2. The formulation of claim 1 wherein the acidic monomer is a carboxylicacid monomer.
 3. The formulation of claim 1 further comprising at leastone solvent.
 4. The formulation of claim 1 wherein the diluent monomeris 2-hydroxyethylmethacrylate (PMGDM).
 5. The formulation of claim 1wherein the photoinitiator is camphorquinone and a tertiary amine. 6.The formulation of claim 1 wherein the acid monomer is pyromelliticglycerol dimethacrylate (PMGDM).
 7. The formulation of claim 1 whereinthe acidic monomer is pyromellitic glycerol dimethyacrylate (PMGDM). 8.The formulation of claim 1 wherein the acidic monomer is pyromelliticdianhydride-HEMA adduct (PMDM).
 9. The formulation of claim 1 whereinthe acidic monomer is biphenyl dianhydride-HEMA adduct (BPDM).
 10. Theformulation of claim 1 wherein the acidic monomer is3,3'-4,4'-tetracarboxylic dianhydride-glycerol dimethacrylate adduct(BDGDM).
 11. The formulation of claim 6 wherein the pyromelliticglycerol dimethacrylate (PMGDM) adhesive resin is made by a processcomprising:reacting 1 part pyromellitic dianhydride (PMDA) and greaterthan 2 parts glycerol dimethacrylate (GDM) to form PMGDM.
 12. Theformulation of claim 6 wherein the diluent monomer is2-hydroxyethylmethacrylate (2-HEMA).
 13. The formulation of claim 7wherein the diluent monomer is 2-hydroxyethylnethyacrylate (2-HEMA). 14.The formulation of claim 7 wherein the diluent monomer is glyceroldimethacrylate (GDM).
 15. The formulation of claim 6 wherein the diluentmonomer is tetrahydro furfurylmethacrylate (THFM).
 16. A single-solutionadhesive resin formulation for bonding a composite resin to enamel,dentin or nonprecious metal, comprising:not more than two polymerizablemonomers, a solvent, and a photoinitiator, wherein a first of the twomonomers is pyromellitic glycerol dimethacrylate (PMGDM) monomer, thesecond of the two monomers is 2-HEMA monomer, and the photoinitiator is2, 4, 6-trimethylbenzoyldiphenylphosphine oxide.
 17. A method ofproducing a single-solution formulation for bonding a composite resin toenamel, dentin, or nonprecious metal, or for bonding a ceramic ornonprecious metal to dentin, comprising the step of:combining not morethan two monomers and an initiator consisting of a photoinitiator,wherein a first of the two monomers is an acidic monomer and the secondof the two monomers is a diluent monomer, wherein polymerization of saidmonomers forms a bond having a shear bond strength of at least 20 MPa.18. The method of claim 17 wherein the acidic monomer is a carboxylicacid monomer.
 19. The method of claim 17 wherein a first of the twomonomers is PMGDM monomer, the second of the two monomers is 2-HEMAmonomer.
 20. The method of claim 19 wherein the photoinitiator is2,4,6-trimethylbenzoyldiphenylphosphine oxide.
 21. The method of claim19 wherein the pyromellitic glycerol dimethacrylate (PMGDM) adhesiveresin is made by a process comprising:reacting 1 part pyromelliticdianhydride (PMDA) and greater than 2 parts glycerol dimethacrylate(GDM) to form PMGDM.
 22. A single-solution adhesive resin formulationfor bonding a composite resin to enamel, dentin or nonprecious metal, orfor bonding a ceramic or a nonprecious metal to dentin, comprising:notmore than two polymerizable monomers and an initiator consisting of aphotoinitiator and a tertiary amine, wherein a first of the two monomersis an acidic monomer and the second of the two monomer is a diluentmonomer, wherein polymerization of said monomers forms a bond having ashear bond strength of at least 20 MPa.
 23. The formulation of claim 22wherein said photoinitiator is selected from the group consisting of2,4,6-trimethylbenzoyldiphenylphosphine oxide and camphorquinone. 24.The formulation of claim 22, wherein said tertiary amine is4-N,N-(dimethylamino) benzoate, said photoinitiator is camphorquinone,said acidic monomer is pyromellitic glycerol dimethacrylate (PMGDM),said diluent monomer is 2-hydroxyethylmethacrylate (2-HEMA).
 25. Theformulation of claim 22, wherein said photoinitiator is selected fromthe group consisting of 2,4,6-trimethylbemzoyldiphenyl phosphine oxideand camphorquinone, said tertiary amine is 4-N,N-(dimethylamino)benzoate (4-EDMAB), said acidic monomer is selected from the groupconsisting of pyromellitic dianhydride-HEMA adduct (PMDM), pyromelliticglycerol dimethacrylate (PMGDM), bipheyl dianhydride-HEMA adduct (BPDM),3,3'-4,4'-tetracarboxylic dianhydride-glycerol dimethacrylate adduct(BDGDM), and5-(2,5-dioxotetrahydro-3-furanyl)-3-cyclohexene-1,2-dicarboxylicanhydride-glycerol dimethacrylateadduct(B4400-GDM), said diluent monomeris selected from the group consisting of 2-hydroxymethacrylate (2-HEMA),glycerol dimethacrylate (GDM), ethyl-α-hydroxymethacrylate (EHMA) andtetrahydro furfurylmethacrylate (THFM).
 26. The formulation of claim 1,wherein said photoinitiator is 2,4,6-trimethylbenzoyldiphenyl phosphineoxide, said acidic monomer is selected from the group consisting ofpyromellitic dianhydride-HEMA adduct (PMDM), pyromellitic glyceroldimethacrylate (PMGDM), biphenyl dianhydride-HEMA adduct (BPDM),3,3'-4,4'-tetracarboxylic dianhydride-glycerol dimethacrylate adduct(BDGCM), and5-(2,5-dioxotetrahydro-3-furanyl)-3-cyclohexene-1,2-dicarboxylicanhydride-glycerol dimethacrylate adduct (B4400-GDM), said diluentmonomer is selected from the group consisting of 2-hydroxymethacrylate(2-HEMA), glycerol dimethacrylate (GDM), ethyl-α-hydroxymethacrylate(EHMA), and tetrahydro furfurylmethacrylate (THFM).
 27. The formulatiomof 22 wherein the photoinitiator is camphorquinone and the tertiaryamine is 4-N,H-(dimethylamino) benzoate.